Unsymmetrical disazo dyestuffs



compound formed .by initial coupling of the Patented Feb. 5, 1952 v r UNITED STATES PATENT j jOFFlCE I 2,584,935 UNSYMMETRICAL DISAZO DYESTUFFS- Albert F. Strobel, Phillipsburg, N. J., and William W. Williams, Easton, Pa., assignors to. General Aniline & Film Corporation, New York, N. Y., a. corporation of New York No Drawing. Application February 4, 1949, Serial No. 74,704

6 Claims. 260-'-175) 1 I This invention relates to novel unsymmetrical disazo diphenylurea dyestuffs, and a method for acetoacetanilide interferes with complete coupling of the diazo-azo compound to form the depreparing the same. sired disazo compound. Thus, preparation of the It is n Object Of h s inv n ion 0 provi present dyestufls can be carried out satisfactorily dy s yielding i ec dy ngs on cellulosic fiber, 5 by adding the tetrazo compound to a mixture especially cotton, from alkaline to neutral dye- (e. g. an aqueous alkaline solution) containing baths, and which upon treatment on the fiber approximately equimolecular amounts of the sul- With lake-forming metal S s, pec al y c pp foacetoacetanilide and the non-sulfoac'etoacet salts, yield colorations of, excellent fastness to anilide, respectively, or by first coupling the washing and light. tetrazo compound with about one molecular The dyestufis mentioned are prepared by couequivalent of the sulfoacetoacetanilide and then pling tetrazotized 4,4-diamino-3,3 dicarboxycoupling the diazo-azo compound with a molecdiphenylurea or -thiourea with one molecular ular equivalent of the non-sulfoacetoacetanilide. equivalent of each of two different aceto- The disazo dyestufi" thus formed can be readily acetanilides, one containing a. sulfo group in the recovered from the reaction mixture in the form anilide nucleus and the other containing no ofafilter cake. water-solubilizing nuclear substituents. Either In order to prepare a dyestuff composition havor both of the acetoacetanilides may contain ing the desired solubility in water, the filter, cake non-water-solubilizing substituents in the aniis acidified with a volatile organic acid, particilide nucleus, particularly halogen, nitro, alkyl, ularly acetic acid, and dried by heating under alkoxy, acetamino, carboxyalkyl or aliphatic reduced pressure (e. g. at temperatures from acyl (i. e.,keto) groups. I 65-75" 0.). Upon grinding the dried dyestuff to The resulting dyestuffs, in the form of their a powder and standardizing with diluents, es free acids, have the following formula: pecially alkaline-reacting ,Salts such as sodium HOOC (iJOOH wherein X represents a member of the group consisting of O and S, R1-SO3H represents a sulfophenyl radical containing no additional water for dyeing purposes.- water-solubilizing substituents (such as sulfo, The dyestuffs of thisinvention are applied for carboxy, amino or hydroxyl groups), and R2 dyeing cellulosic fiber or textile material such as represents a phenyl radical containing no watercotton or regenerated cellulose, directly in aquesolubilizing substituents of the aforesaidtype. ous neutral to alkalinedyebaths. The dyed ma- The preferred dyestuffs of this invention are terial is preferably after-treated with a lakethose having in free acid form the following forforming metal salt, especially a copper salt such carbonate and disodium phosphate, dyestuff powders are obtained having-excellent solubility. in

mula: 40 as copper sulfate, whereby optimum fastness H000 coon x CHi-CO-CHN=N NH -NH N=NCHCOCH;

l l SOaH l i awn- 1; ONH@ Y 7 wherein X has the same significance as given properties are obtained. The dyestuffs yield yelabove, and Y and Z represent members of the low to orange to brown'shades in the aforesaid group consisting of hydrogen, halogen, nitro, aldyeing processes. The present dyestuffs are eskyl (methyl, ethyl), alkoxy (methoxy, ethoxy), pecially adapted for dyeing the cellulosic comacetamino, carboxyalkyl (carboxymethyl, carponent of mixed fabrics of cellulosic fiber and boxyethyl) and aliphatic acyl (CH3CO) groups. organic derivatives of cellulose v(e. g. cellulose In preparing the dyestuffs of this invention, it acetate), since the dyestuffs of this invention is desirable to avoid coupling of the tetrazotized leave the organic derivativeof cellulose mate- 4,4' diamino 3,3 dicarboxy diphenylurea rial unstained. In addition, the colorations proor -thiourea with the non-sulfoacetoacetanilide duced on cellulosicfiber, when after-treated with before coupling occurs with the sulfoacetoacetcopper salts, yield a clear alkaline discharge, for anilide, since the insolubility of the diazo-azo example, with alkaline hydrosulfite discharge compositions.

tetrazo' compound with the non-sulfo substituted It was known heretofore to prepare asymmetrical .disazo dyestuffs from, tetrazotized: 4,4- diamino-3,3-dicarboxy-diphenylurea or -thiourea, by coupling with two different acetoacetaniq lides both of which, however, contain. av sulfo group. For example, one of the dyestuffs, heretofore employed in commercial ydyeing; isob'- tained by coupling tetrazotized-gipi -diaminofifidicarboxy-diphenylurea with'one molecular equiv-.' alent of 4-sulfoacetoacetanilide and one molecular equivalent of 2-chloro-5-sulfoacetoacetanilide; the resulting dyestuff yielding yellow shades'on cotton, particularly when after-treatedwith cop'- per sulfate. As compared with this dyestuff, the dyestuffs of thee-present 1 inventionnareg equally soluble; inaqueous, alkaline to neutral. dyebaths, despite the-fact that they contain. only one rather than, twosulfm groups. In. dyeing. cellulosic fibers sucln as cotton, -the-dyestuffs ,Ofl, ,this invention, exaus 'mq e rapidlaand more u l j om. alkaline to; neutral dyebaths i than v the disulfo, dyestufi the-;p ior. art,. indicating superionisubstantiyity m1: e lulosic materials- When aIter-LtI atQd-Qn the fiber witht ,a copper salt, the. dyestuffs of, this Invent o y e dzcolqrations whlch-anebrishten hadea n sv'vi hihax su e iors-we ss t iwashz ing wlthyaqueousisoap; or soda,.ash, solutions. as comparedwith the icorrespondingcolorations produced with: tha-atoresaid. ,disulfo disazoi dyestuff. The coloration produced by coppering-theaforee said; disu1onated di sazo dyestuiipn qcell'ulosic fiber leaues a, yellow, stain when treated. with an alkaline dischargerwhereasthe colorations similarly-produced by after-coppering the. dyestuffs ofpthisinuentiomyielda perfectly clear, discharge. Preparatiomof amumber,otpiteferred-dyestufls of this ,invention,is. il111stitated.,in:,the following exauml swherein; parts .andpercentages. ar by weight unless otherwise indicated, parts by volume signifying the volume of an equal number of parts by weight of water.,

Example 1 27.25 parts of 4,4'-diamino-3,3"-dicarboxy diphenylurea -in the-formof--a--5 aqueous 'paste are dissolved -in-a mixture "of--30-par-ts by-volume of 50% aqueous caustic'soda--and*=350' parts' of water; 114 parts-by-volume-of-=%'iaqueous sodium 'nitrite are added, and the resulting somtion -is-cooled to' 0 10* C9 The solution is added ina' fine-stream tea-thoroughlyagitatedmixture of -75 parts'by volume-ofconcentrated-hydrochloric acid with *200'-parts of-"ice; the final tem'-- perature of-the'm'rxture being abeut=8 G; Agitation is continued for one-half hour while cooling to maintain a temperature of 0-5 C. A coupling solution is prepared by dissolving: 14.-2 pants-of=- acetoacetanilide and 34.9 parts of a 72% aqueous paste of 4-sulfo-2-chloroacetoacetanilide in a mixture of 100 parts of water and/'25" parts by volume of 40% sodium hydroxide. 25 parts of sodium bicarbonate are added, whereby the acetoacetanilide' is ipre'cipitated-u and then 530 pantssby volume i=oi;-?% aqueousi sodiumcarbonate are added and'i themesulting solution: is cOoleditoO 5= C." The itetrazosolution,- first prepared,":is added-portionw-isepver a p'eriod of about one hour i to .-the-.-coupling solution while 1 maintaining itheatemperatureiat 0-530." The coupling mixture yields. atnegative testoforx diazo compounds -wl'ienitreated with Heacidiz. about one. minute-after the iaddition -ofzieach :portionof the solution. When all of thea tetrazorsoluti'on vhas beenfi added, the: resulting slurry is agitated for two hours at 5 0., andsthenrfiltered tdreeover the dyestuitfr The" filter cake is slurried :xbeing 111.6 parts For standardization, 79 parts of -the resulting dyestufi powder is mixed in a ballmill, with: 50 parts of sodium carbonate, 25 parts of disodium phosphategand 2 parts of Nekal BX (anv alkylated naphthalene sulfonate wetting agent),.- The resultingdyestufl' jcomposition has good solubility in water, dyeing, cotton yellow shades. from aqueousalkaline to neutral dyebaths, whichhupon after-treatment with aqueous copper sulfate, .acquireexcellent fastness to washing.

.The resultingdyestufil produces no stain on cellulose., ace.tate material. The coloration ,produced y oppering the ,dyestuff .or this example oncotton possesses superior brilliance of shade and fastness to washing as comparedwith, av dyestuff obtained, by coupling the sametetrazo compound onthe one hand with p -sulfoacetoacetanilide and onrthe other-hand with 2-,chloro-5'-sulfoacetoacetanilide. The coloration produced by coppering the dyestufi of,-this example on cotton. fiber yields. a cleardischarge when treated with ,an alkaline hydrosulfite composition, while the aforesaid commercial, dyestuif leaves a yellow stain on similar discharge treatment. The dyestuiffofthis exampleiurth'er. has similar solubility in aqueous alkaline to neutralfdyebaths as compared with the aforesaid'disulfodyestuffhand exhausts. more. rapidly and more fully on cotton than the aforesaid commercial dyestuff.

Example-2 7.34 parts of 4,4'-diamino-3,3.'-dicarboxy-diphenylurea in the form of a 5% aqueous paste is rendered alkaline by mixing with 15 parts-by volume of 40% aqueous caustic soda,whereuppn 30.7 parts by volume-of "10% aqueous-sodium nitrite areadded to the mixture. The resulting solution is'gradually poured (in about 20 minutes) into a mixture of 25 parts by volume of concentrated hydrochloric acid with parts of ice. After-agitating for 15 minutes, the resulting slurry is filtered, and the tetrazo filter cake is thoroughly mixed with 6.36 parts of 5-sulfo-2 methoxy-acetoacetanilide. 30' parts of sodium bicarbonate are addedwith thorough agitation and the mixtureis-kneaded: for -2 hours. 4.25 parts-of acetoacetanilide are incorporated with the mixture by thorough kneading. 11 parts by volume of 40% aqueous sodiumhydroxide are worked into the resulting paste, and after kneading for one hour, the product is slurried with-200: parts of water-acidified with 25 parts: by volume-of glacial:.iacetic' acid.- The resulting slurryis filtered, and :the filter cake is dried. un der reduced pressure in a vacuumoven at about 70 C. Standardization is carried out in the same manner as in Example-1. The resulting dyestuif has solubility and exhaust properties oncotton similar to those possessed by the dyestuif'ofEx amplei l, and yields. yellow shades oncotton which, after coppering :with' copper sulfateyhave outstanding :fastness: to washing and light: The resulting'dyestuff, like the-product of Example 1, ischaracterized by the: absencezof staining eflecttowards --4celluloseacetate" materials and atter lides which are suitable for use as coupling components in making the dyestuffs of this invention are, the acetoacetyl derivatives of the following sulfonated aniline compounds:

sulfanilic acid orthanilic acid 5-su1fo-o-anisidine 5-sulfo-2-chloroaniline 2-sulfo-3-chloroaniline 2-sulfo-4-chloroaniline 2-sulfo-4-bromoaniline 6-sulfo-3-nitraniline 3-sulfo-4-chloroanisidine 4-sulfo-2-nitraniline v 2-sulfo-4-acetaminoaniline 3-sulfo-p-toluidine 2-sulfo -5-nitro-p-toluidine p-sulfo-o-toluidine 2-su1fo-5-chloro-p-anisidine 3-sulfo-p-phenetidine As indicated above, it is important in preparing the disazo dyestuifs of the invention that the coupling be carried out under conditions preventing coupling of the tetrazotized diaminodicarboxy-diphenylurea with the unsulfonated acetoacetanilide before coupling occurs with the sulfo substituted acetoacetanilide. Suitable conditions for obtaining the desired coupling with 1 2.0 mol each of the two acetoacetanilide compounds are illustrated in the examples, wherein the tetrazo compound is added progressively to a solution of both coupling components, or wherein the coppering with a copper sulfate solution on the fiber, yields a clear alkaline discharge.

Example 3 A disazo dyestufi is prepared in the same manner as in Example 1, except that instead of 4- sulfo-2-chloroacetoacetani1ide and acetoacetanilide itself, equivalent amounts of 4-sulfo-2- methoxy-acetoacetanilide and of 2-chloroacetoaoetanilide are respectively employed. A yellow dyestufi yielding brilliant colorations on cellulosic fiber directly from aqueous to alkaline dyebaths which are slightly redder than those produced with the dyestuff of Example 1, and having similar dyeing and fastness properties to those of the product of Example 1, is obtained.

In each of the foregoing examples, 4,4- diamino-3,3'-dicarboxy-diphenyl-thiourea can be substituted for the corresponding urea employed on as the tetrazo compound, whereby dyestufls having similar color and fastness'properties are obtained.

Instead of the acetoacetanilides of the examples, other acetoacetanilides can be used. Thus, acetoacetanilides containing no sulfonic acid or other water-solubilizing groups can be prepared by reacting acetoacetic acid ethyl ester or diketene in a solvent such as benzene with aniline or unsulfonated nuclear substitution products thereof which contain no water-solubilizing groups. The resulting products, suitable as coupling components in preparing the dyestuffs of this invention, are for example, the acetoacetyl derivatives tetrazo compound is first added to the sulfo of the following amines acetoacetanilide and the intermediate diazo-azo aniline compound thereby formed is then coupled with 2-chloroaniline the non-sulfoacetoacetanilide. 2-methyl-3-chloroaniline Variations and modifications which will be obo-toluidine vious to those skilled in the art can be made in p-nitraniline 40 the foregoing processes and products without depor m-amino-acetophenone parting from the scope or spirit of the invention. p-bromoaniline We claim:

1. An unsymmetrical disazo dyestuff having, in the form of its free acid, the following formula:

HOOC (30011 C O-NHR: O-NH-Ry-SO H wherein X represents a member of the group consisting of oxygen and sulfur, Ri-SO3H is a sulfo phenyl radical containing no additional watersoiubilizing substituents, and R2 is a phenyl radi- Nuclear sulfo substituted acetoacetanilides cal containing no water-solubilizing substituents. P y a the other coupling Component for 2. An unsymmetrical disazo dyestuif having, in paring the dyestuffs of this invention are best the form of its free acid, the following formula:

H o o 0 o 0 OH 2,4-xylidine o-anisidine p-amino-ethyl-benzoate m-amino-methyl-benzoate p-amino-acetanilide Owl 0 prepared by reacting diketene with the corre- 3. An unsymmetrical disazo dyestuif having, in sponding sulfonated aniline. Sulfoacetoacetanithe form of its free acid, the following formula:

HOOC COOH l 0-NH CHgO agusagcsa -42 An'un'symm'etricai disazo dyestufi havlng'; in the form of 11ts freecacid,i the following formula:

acetanilid containin'g mo water-'solubilizingi substituents, .an'd' recoveringuthe" dy'estufl from the 5. Process of preparin'g'an unsymmetrical disazo dyestuff, which comprises coupling a member of the group consisting oftetrazotized 4,4'-diamino-3,3-dicarboxy diphenylurea and tetrazotized 4,4diamin'o-3,3' dicarboxy diphenylthiourea with one molecular'equivalent of an acetoacetanilidecontaining a nuclear sulfo group but no additional water-'solubilizing substituents, and one molecular equivalent of an acetoacetan' ilide containing no water-'solubilizing substituents; wherein thetetrazo compound is added to a mixture of said acetoacetanilides in' anaqueous alkaline reaction mixture, and theresultingrcouplingreaction'allowed to proceed until no free tetrazo' compound remains in the'reaction mixture:

6. In aprocess for preparing adisazo' dyestuif involvingcoupling'in aqueous alkaline medium of a member'of the-group: consisting of 'tetr'azotized 4,4-diamino-3,3 -dicarboxy diphenylurea and tetrazotized 4,'4-diamino-3,3-dicarboxy-diphenyl-thiourea with one molecular equivalent of an acetoacetanilide containing a nuclear sulfogroup butno additional water-'solubilizing 'substituents and with one molecular-equivalent of an aceto- Number Name Date 946,051 Kahn Jan. 11, v1910 946L052 Kahn' Jahill, 1910 1,078,503 Herzbergl NOV; 11, 1913 1,851,097 Hentrich et 'al'. Mar.'29, 1932 2,427,537 straub'et al'. Sept. 16,.1947

2,476,259 Mayer etall Ju1y'f12; 1949 FOREIGN PATENTS Number Country" Date I 215,769 Great Britain-' June 18,1925 285,812 Great Britain May 15, 1929 

2. AN AUNSYMMETRICAL DISAZO DYESTUFF HAVING, IN THE FORM OF ITS FREE ACID, THE FOLLOWING FORMULA; 